CrIII(porphyrinato)(Cl)(H2O) | 169335-22-2

• 英文名称: CrIII(porphyrinato)(Cl)(H2O)
• 英文别名: (aqua)(chloro)(5,10,15,20-tetraphenylporphyrinato)chromium(III)；aquachloro(5,10,15,20-tetraphenylporphyrinato)chromium(III)；chloro(5,10,15,20-tetraphenylporphinato)chromium(III)；chloroaquachromium(III) tetraphenylporphyrin；(aqua)(chlorido)(porphyrinato)chromium(III)；Cr^III(porphyrinato)(Cl)(H₂O)；Cr^III(TPP)(Cl)(H₂O)
• CAS: 169335-22-2
• 化学式: C₄₄H₃₀ClCrN₄O
• 分子量: 718.197
• InChiKey: XZWOYGLLGIROII-NBICUONBSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  CrIII(porphyrinato)(Cl)(H2O) 以 甲苯 为溶剂， 生成 chloro(5,10,15,20-tetraphenylporphyrinato)chromium(III)
  参考文献：
  名称：

  Monoligated Chloro(5,10,15,20-tetraphenylporphinato)chromium(III)在甲苯中的激光光解产生的五配位中间体的反应性

  摘要：

  对于两个反应，轴向配体重组反应的速率常数在 25.0 °C 时都落在 1 × 109 mol−1 kg s−1 左右的狭窄范围内。激活参数指示...

  DOI：

  10.1246/bcsj.68.2293
• 作为产物：
  描述：

  盐酸 、 Cr(II)(meso-tetraphenylporphyrinato) 、 水 在 氧气 作用下， 生成 CrIII(porphyrinato)(Cl)(H2O)
  参考文献：
  名称：

  Dual Application of (Aqua)(Chlorido)(Porphyrinato)Chromium(III) as Hypersensitive Amine-Triggered ON Switch and for Dioxygen Activation

  摘要：

  Although synthesis and substitution reactions of chlorido chromium(III) porphyrins Cr-III(TPP)(Cl)(L) (H2TPP = 5,10,15,20-tetraphenyl porphyrin, L = pyridine, H2O, ROH, etc.), have been well-established in coordination chemistry for decades, an unexpected dichotomous reactivity of Cr-III(TPP)(Cl)(H2O) (1) toward amines is disclosed here. This reactivity leads to the application of 1 as highly sensitive substoichiometric and irreversible ON switch for amine detection by an autocatalytic pathway. The concomitant activation of O-2 by the 1/amine system is furthermore exploited in an electrochemically driven epoxidation of norbonene using O-2 as initial oxidant.

  DOI：

  10.1021/ic501644z

文献信息

• Laser Photolysis of Chromium(III) Porphyrins with Axial Pyridines in Dichloromethane and Toluene Solutions. Novel Effects of a Hydrogen Bond in the Ligand Exchange Reaction
  作者：Masahiko Inamo、Hideyuki Nakaba、Kiyohiko Nakajima、Mikio Hoshino

  DOI：10.1021/ic0002059

  日期：2000.10.1

  H2O to give [Cr(TPP)(Cl)(H2O)], which eventually exchanges the axial H2O with Py to regenerate [Cr(TPP)(Cl)(Py)]. The rate for the ligand exchange of [Cr(TPP)(Cl)(H2O)] with exogenous Py is found to exhibit a bell-shaped pyridine-concentration dependence. Kinetic studies revealed that at a high Py concentration, the exogenous Py probably makes a hydrogen bond with the axial H2O of [Cr(TPP)(Cl)(H2O)] to

  在含有二氯甲烷和甲苯的水中对 (氯)(吡啶)(5,10,15,20-四苯基卟啉)铬 (III), [Cr(TPP)(Cl)(Py)] 进行了激光光解研究。吡啶从 [Cr(TPP)(Cl)(Py)] 光诱导解离产生的五坐标 [Cr(TPP)(Cl)] 最初与 H2O 反应生成 [Cr(TPP)(Cl)( ) ]，最终将轴向 与 Py 交换以再生 [Cr(TPP)(Cl)(Py)]。发现 [Cr(TPP)(Cl)( )] 与外源 Py 的配体交换速率表现出钟形吡啶浓度依赖性。动力学研究表明，在高 Py 浓度下，外源 Py 可能与 [Cr(TPP)(Cl)( )] 的轴向 形成氢键，生成 [Cr(TPP)(Cl)(HO-H· ··Py)] 作为一个死胡同复合体。通过 X 射线结构分析确定了具有通过氢键与配位 配体结合的 2-甲基吡啶分子的 Cr-TPP 复合物
• Effect of the axial halogen ligand on the substitution reactions of chromium(III) porphyrin complex
  作者：Kikuko Okada、Atsumi Sumida、Rie Inagaki、Masahiko Inamo

  DOI：10.1016/j.ica.2012.04.001

  日期：2012.9

  kinetics of the substitution reaction of the chromium(III) complex of 5,10,15,20-tetraphenylporphyrin, [Cr(TPP)(X)(L)] (X = F, Cl, Br), where L represents a non-charged ligand such as H2O, pyridine, or 1-methylimidazole, was investigated. The present study aimed to elucidate the effect of the axial halogen ligand, X on the substitution reaction of the ligand trans to X. The substitution reaction of the

  摘要5,10,15,20-四苯基卟啉[Cr（TPP）（X）（L）]（X = F，Cl，Br）的铬（III）配合物的取代反应的热力学和动力学，其中研究了L代表不带电荷的配体，例如H 2 O，吡啶或1-甲基咪唑。本研究旨在阐明轴向卤素配体X对配体向X的取代反应的影响。[Cr（TPP）（X）（Py）]的轴向吡啶配体被1-取代的反应在二氯甲烷中分光光度法研究了甲基咪唑，发现该反应是通过有限的离解机理进行的，并且对于氟络合物[Cr（TPP）（F）（Py）]，吡啶离解的活化焓要小得多。比氯络合物[Cr（TPP）（Cl）（Py）]，即ΔH‡= 57.5±1.1和97.2±1.4 kJ mol-1，分别。根据卤素配体对[Cr（TPP）（X）（L）]的轴向配体取代反应的反式作用来讨论这些结果，并得出结论，键的强度显示了Cr–的趋势。 F> Cr–Cl> Cr–Br，导致F−配体的强反式作用。
• Femtosecond time-resolved photo-absorption studies on the excitation dynamics of chromium(III) porphyrin complexes in solution
  作者：Masahiko Inamo、Chie Okabe、Takakazu Nakabayashi、Nobuyuki Nishi、Mikio Hoshino

  DOI：10.1016/j.cplett.2007.07.079

  日期：2007.9

  The electronic relaxation dynamics of the excited states of the chromium(III) tetraphenylporphyrin complexes, [Cr(TPP)(Cl)(L)] (L = H2O, pyridine, 1-methylimidazole), in toluene were studied by using femtosecond time-resolved absorption spectroscopy. The excited state (4T1) of 1-methylimidazole and pyridine complexes given by a very rapid intersystem crossing from 4S1 to 4T1 decays to establish the

  飞秒研究了铬（III）四苯基卟啉配合物[Cr（TPP）（Cl）（L）]（L = H 2 O，吡啶，1-甲基咪唑）在甲苯中的激发态电子弛豫动力学时间分辨吸收光谱。激发态（4 Ť 1 1-甲基咪唑），并从通过非常快速的系间窜越给予吡啶络合物4 š 1至4 Ť 1衰变来建立4 Ť 1  ⇌  6 Ť 1在几百皮秒平衡。的4 Ť 1个的[CR（TPP）（CL）（H状态2O）]表现出双指数衰减，该衰减由轴向H 2 O配体的光解离过程和[Cr（TPP）（Cl）]基态的光解中间产物的衰减组成。
• Laser-Photolysis Studies of Isocyanide Complexes of Chlorochromium(III) Tetraphenylporphyrin in Toluene Solutions
  作者：Mikio Hoshino、Takahiro Nagamori、Hiroshi Seki、Teiji Chihara、Takahiro Tase、Yasuo Wakatsuki、Masahiko Inamo

  DOI：10.1021/jp9725902

  日期：1998.2.1

  Chloroaquachromium(III) tetraphenylporphyrin, Cl(H2O)(CrTPP)-T-III, reversibly reacts with isocyanide, CN-R, to form Cl(CN-R)(CrTPP)-T-III in toluene solutions containing 4.4 x 10(-3) M H2O and CN-R. The equilibrium constant for the formation of CI(CN-R)(CrTPP)-T-III obtained by spectroscopic measurements ranges from 10 to 10(2) depending on the nature of the isocyanide used. The laser-photolysis studies of the toluene solution demonstrate that CN-R is photodissociated from Cl(CN-R)(CrPP)-P-III to produce (ClCrTPP)-T-III with a quantum yield ca. 0.1. The five-coordinate (ClCrTPP)-T-III reacts with H2O and CN-R to give Cl(H2O)(CrTPP)-T-III and Cl(CN-R)(CrTPP)-T-III, respectively. The transient product Cl(H2O)(CrTPP)-T-III further reacts with CN-R to regenerate Cl(CN-R)(CrTPP)-T-III. The rates for the decay of Cl(H2O)(CrTPP)-T-III are measured as a function of the concentration of CN-R in order to determine the rate constants of the forward and backward reactions for the formation of Cl(CN-R)(CrTPP)-T-III. The equilibrium constants obtained from the kinetic analysis for the decay of Cl(H2O)(CrTPP)-T-III are in good agreement with those determined by spectroscopic measurements. The mechanism for the equilibrium reaction is discussed in detail on the basis of the rate constants for the formation of Cl(H2O)(CrTPP)-T-III and Cl(CN-R)(CrTPP)-T-III from (ClCrTPP)-T-III, measured in the temperature range 200-300 K. The quantum yield for the photodissociation of CN-R is not affected by the presence of oxygen. Since the lowest excited state T-6(1) Of Cl(CN-R)(CrTPP)-T-III observed by laser photolysis is effectively quenched by oxygen, this state is not responsible for the ligand ejection from CI(CN-R)(CrTPP)-T-III. The S-4(1) State is assumed to be the reactive excited state of Cl(CN-R)(CrTPP)-T-III.